CN114783641A - Application method of polyion liquid gel material in uranium rhenium adsorption separation - Google Patents

Application method of polyion liquid gel material in uranium rhenium adsorption separation Download PDF

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CN114783641A
CN114783641A CN202210322606.1A CN202210322606A CN114783641A CN 114783641 A CN114783641 A CN 114783641A CN 202210322606 A CN202210322606 A CN 202210322606A CN 114783641 A CN114783641 A CN 114783641A
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rhenium
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赵龙
缪昕颖
花榕
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Huazhong University of Science and Technology
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Abstract

The invention belongs to the field of adsorption and recovery of rare metal elements, and discloses an application method of a polyion liquid gel material in uranium rhenium adsorption separation. In particular, the + 7-valent rhenium element Re+7And/or the + 6-valent uranium element U+6The polyion liquid gel exists in an anion form, and the polyion liquid gel material is alkenyl imidazole type polyion liquid gel; the application is specifically that the alkenyl imidazole type polyion liquid gel is added into a solution to be treated so as to carry out adsorption and enable the solution to contain Re+7And/or contain U+6The anion is adsorbed to the polyion liquid gel material to realize adsorption separation. The invention uses alkenyl imidazole type with specific structural general formulaThe polyion liquid gel can be prepared by adding alkenyl imidazole type polyion liquid gel into a solution containing rhenium or uranium to adsorb rhenium or uranium in the solution mainly by anion exchange, so that adsorption separation of rhenium and uranium is realized, and selective adsorption separation of rhenium in a uranium-rhenium system can be especially realized.

Description

Application method of polyion liquid gel material in uranium rhenium adsorption separation
Technical Field
The invention belongs to the field of rare metal element adsorption and recovery, and particularly relates to an application method of a polyion liquid gel material in uranium-rhenium adsorption and separation.
Background
Uranium ore leachate contains various metal elements such as uranium, rhenium, iron, aluminum, calcium, magnesium and the like, and has immeasurable value. Uranium (U) itself is a rare element having radioactivity and is also an important fuel of nuclear energy, and is used in large quantities in nuclear power plants due to its good economic efficiency. However, the large-scale exploitation of uranium ores and the powerful development of nuclear energy not only cause the rapid reduction of uranium resources, but also generate a large amount of radioactive solid wastes such as waste rocks and tailings, and cause the problem of leaving behind uranium pollution in water environments. Rhenium (Re) is also a rare metal element and is present in the earth's crust in a very small amount, about 10-7%. Rhenium and its compounds also have excellent catalytic activity, so it has important application in petrochemical industry and other industries. And its industrial application is irreplaceable in many cases, and thus is regarded as an extremely precious scarce metal. Uranium ore has proven to be a promising feed for rhenium production. It has been reported that since 1986, the hassakstan researchers began recovering valuable rhenium and uranium resources from uranium ores, and other countries such as russia, uzbekistan, usa, etc. have also conducted research on extracting rhenium from underground uranium leach solutions. Relatively less research is carried out on the separation and recovery process of uranium rhenium resources in uranium ores in China. At present, rhenium resource accompanying is found in placentable sandstone-type uranium ores of Tianshan uranium industry in Xinjiang and Tongliao uranium ore in Nemonton. Although the rhenium concentration in the underground leaching solution of the uranium ore is very low (0.25-0.5 mg/L), the quantity of rhenium is not small and has great value in utilization. Therefore, how to effectively separate uranium rhenium from leaching solution containing uranium rhenium is a problem to be faced for realizing the maximization of resource utilization.
At present, methods for recovering rhenium and uranium from an aqueous solution mainly comprise a precipitation method, a solvent extraction method and an adsorption method. Wherein, the selectivity of the chemical precipitation method is poor, and various metal ions are difficult to separate; the solvent extraction method has complex process, uses a plurality of toxic and volatile solvents, and is easy to cause secondary pollution; adsorption is considered one of the most effective methods due to its low cost, good selectivity and simple process. In recent years, the separation and recovery of uranium and rhenium by using adsorbents have been studied, but most of the adsorbent materials have some defects, such as less kinds of adsorbents, large amount of non-functional matrixes in the adsorbents, incapability of combining adsorption capacity and rate and high cost.
The ionic liquid is a commonly used green solvent, and has been widely researched in the field of metal separation due to high stability, designable structure and functional groups. The application of the existing ionic liquid in metal recovery and separation is mainly divided into the following steps: firstly, the extract is used as a free component to participate in an extraction system, but the application range of the extract is greatly limited by the liquid state, and the problems of leaching, excessive consumption and recovery exist in the use process; in addition, ionic liquids are also commonly grafted onto some solid substrate (i.e., immobilized ionic liquids) to prepare uranium rhenium adsorbents, which are mainly resins and nanomaterials, such as prior art Recovery of ruthenium from sulfuric acid solution by TOPO-imprinted silica adsorbents (DOI:10.1080/01496395.2020.1718709) and silica ionization of cationic urea (VI) and anionic ruthenium (VII)) by graphene oxide-poly (ethylene) adsorbents, a batch, XPS, EXAFS, and DFT bonded adsorbents (DOI:10.1039/C8EN 00677F). Although the recovery performance of the solid-supported ionic liquid adsorbent on metal is better than that of free ionic liquid, the performance of the adsorbent is still generally limited by non-functional matrixes, and further, most of the researches are limited to the single adsorption and enrichment of rhenium or the single adsorption and enrichment of uranium from a solution (rhenium and uranium selective separation in a rhenium and uranium system is not involved), or the simulation of the recovery performance of rhenium and uranium in high-level radioactive waste liquid99Technetium (C)99Tc) or separating rhenium from nickel, molybdenum, platinum and the like, and there is little research on the separation and recovery of uranium rhenium. The polyion liquid gel is a gel combining the self functional advantages of the ionic liquid and the gelThe solid material with a three-dimensional network structure can achieve high adsorption capacity and can easily realize rapid adsorption kinetics. Polyionic liquid gels have been reported for use in adsorbing rhenium for evaluation of shower waste water from nuclear facilities99Recovery of technetium, and application of polyion liquid gel to separation of uranium and rhenium in uranium ore leachate has not been reported.
Disclosure of Invention
In view of the above defects or improvement needs of the prior art, the present invention aims to provide an application method of a polyionic liquid gel material in uranium-rhenium adsorption separation, wherein through the use of an alkenylimidazole polyionic liquid gel with a specific structural general formula, rhenium or uranium in a solution containing rhenium or uranium can be adsorbed mainly by anion exchange by adding the alkenylimidazole polyionic liquid gel, so that rhenium and uranium adsorption separation is realized. The imidazole type polyion liquid gel provided by the invention only consists of ionic liquid, has high density of functional groups (namely imidazole rings), has a three-dimensional porous network structure, has high adsorption capacity on rhenium and uranium, and can realize very quick adsorption balance. On the other hand, it is more important that the adsorbent is capable of selectively separating rhenium from a solution to be treated (uranium mining acid process leach solution) containing rhenium and uranium simultaneously. The method has the advantages of simple and convenient operation, resource saving, economy and environmental protection, and good reusability of the adsorbent.
To achieve the above object, according to the present invention, there is provided a polyion liquid gel material for use in adsorptive separation of rhenium and/or uranium, characterized in that the +7 rhenium element Re+7And/or the + 6-valent uranium element U+6The existing form in the aqueous solution comprises anions, and the polyion liquid gel material is specifically alkenyl imidazole type polyion liquid gel, and the structural formula of the polyion liquid gel is shown as the following formula:
Figure BDA0003570709880000031
in the formula, m and n are independently selected from integers between 1 and 12; x ═ Cl, Br, NO3,BF4,NTf2,PF6；
The application is specifically that the alkenyl imidazole type polyion liquid gel is added into a solution to be treated so as to carry out adsorption and enable the solution to contain Re+7And/or contain U+6The anions of (2) are adsorbed to the polyion liquid gel material to realize adsorption separation.
As a further preference of the present invention, the solution to be treated contains rhenium element; before application, firstly, regulating and controlling the pH value of a solution to be treated to be 2-12; when in use, the polyion liquid gel material can adsorb Re-containing materials+7To effect separation of rhenium from the solution.
As a further preference of the present invention, the solution to be treated contains uranium; before application, firstly, regulating the pH value of a solution to be treated to 5-12; when in use, the polyion liquid gel material can adsorb U-containing substances+6The uranium is separated from the solution.
As a further preference of the present invention, the solution to be treated contains both rhenium element and uranium element; when the method is applied, the pH value of a solution to be treated is regulated to 2-4; when in use, the polyion liquid gel material can selectively adsorb Re-containing materials+7The rhenium and the uranium are separated;
preferably, the solution to be treated is uranium ore leaching liquid.
As a further preference of the invention, after the adsorption is completed, the method further comprises the steps of eluting and separating the correspondingly obtained polyion liquid gel material adsorbed with the target anions by using an eluent so as to regenerate the polyion liquid gel material; the regenerated polyion liquid gel material can be repeatedly applied to rhenium and/or uranium adsorption separation;
preferably, the eluent is HNO with the concentration of 0.1-4 mol/L3Solution or HCl solution with the concentration of 0.1-4 mol/L.
In a further preferred aspect of the present invention, the alkenyl imidazole type polyion liquid gel is obtained by polymerizing and crosslinking an alkenyl-containing imidazole type ionic liquid monomer and a crosslinking agent; wherein, the first and the second end of the pipe are connected with each other,
the cross-linking agent is selected from any one of alkene ionic liquid containing double C-C bonds and alkene chemical cross-linking agent containing double C-C bonds; preferably, the vinyl ionic liquid containing a double C ═ C bond is 1-allyl-3-vinylimidazolium salt, or 3,3 '-divinyl-1, 1' (1, 6-hexanediyl) diimidazolium salt; the alkene chemical cross-linking agent containing double C-C bonds is a divinyl alkyl chemical cross-linking agent or a divinyl benzene chemical cross-linking agent;
the polymerization crosslinking is specifically radiation crosslinking, and is to generate free radicals by inducing C ═ C bonds, and then further initiate polymerization and crosslinking between molecular chains of ionic liquid monomers and crosslinking agents, so that polyion liquid gel is formed.
As a further preferred aspect of the present invention, the alkenyl group-containing imidazole-type ionic liquid monomer is 1-vinyl-3-methyl-imidazole bromide salt, 1-vinyl-3-methyl-imidazole chloride salt, 1-vinyl-3-methyl-imidazole nitrate salt, 1-vinyl-3-methyl-imidazole tetrafluoroborate salt, 1-vinyl-3-methyl-imidazole hexafluorophosphate salt, 1-vinyl-3-methyl-imidazole bistrifluoromethylsulfinate salt, 1-vinyl-3-ethyl-imidazole bromide salt, 1-vinyl-3-ethyl-imidazole chloride salt, 1-vinyl-3-ethyl-imidazole nitrate salt, 1-vinyl-3-methyl-imidazole bromide salt, 1-vinyl-3-ethyl-imidazole chloride salt, or a salt thereof, 1-vinyl-3-ethyl-imidazole tetrafluoroborate, 1-vinyl-3-ethyl-imidazole hexafluorophosphate, 1-vinyl-3-ethyl-imidazole bistrifluoromethylsulfinate, 1-vinyl-3-propyl-imidazole bromide.
As a further preference of the present invention, the polymerization crosslinking reaction is specifically carried out in an aqueous solution, ethanol, methanol, DMSO, or DMF solution, and the reaction temperature is normal temperature; before polymerization crosslinking occurs, the concentration of the imidazole type ionic liquid monomer containing alkenyl in a solution system is 6-80 wt%.
As a further preference of the invention, the radiation crosslinking is in particular carried out using60Co gamma-rays, electron beams or X rays, wherein the irradiation dose is 10-300 kGy; the gel fraction of the polyion liquid gel obtained by the method is more than 60%.
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
1) the alkenyl imidazole type polyion liquid gel provided by the invention can comprehensively recover rhenium and uranium and can be used in a wider acid-base range. Different from the immobilized ionic liquid, the invention adopts the polyionic liquid gel with a specific chemical structure, and the polyionic liquid gel only consists of the ionic liquid, and has high density of functional groups (namely imidazole rings), so that the polyionic liquid gel has high adsorption capacity on rhenium and uranium. The polyion liquid gel has a three-dimensional porous network structure, and is beneficial to the flow of rhenium and uranium ions in the gel, so that the polyion liquid gel has a higher adsorption speed on rhenium and uranium. The alkenyl imidazole type polyion liquid gel adsorbs rhenium or uranium in solution through anion exchange (rhenium or uranium exists in the form of Re (VII) and U (VI) anions in the solution respectively), has very fast adsorption rate, and can reach equilibrium within 1min and 4min respectively. The alkenyl imidazole polyion liquid gel provided by the invention only uses the imidazole ring with positive charges as an adsorption group, but cannot adsorb metal ions with positive charges, and is particularly suitable for uranium ore pickle liquor containing rhenium.
2) According to the invention, rhenium in the uranium ore acid process leaching solution containing rhenium can be selectively separated by utilizing the alkenyl imidazole type polyion liquid gel, during the specific operation, the pH value of the solution to be treated (such as the uranium ore leaching solution) can be firstly adjusted to 2-4 (of course, if the pH value of the initial solution meets the condition, no pH regulating agent needs to be added), and the rhenium can be selectively adsorbed and separated by utilizing different ion forms of the uranium and rhenium in the solution. Namely, the alkenyl imidazole polyion liquid gel provided by the invention can selectively adsorb associated rhenium in the rhenium-containing uranium ore pickle liquor.
3) The alkenyl imidazole type polyion liquid gel disclosed by the invention is simple in preparation method, easy to control conditions, low in energy consumption, safe and environment-friendly, and suitable for mass production. The invention also preferably designs the synthesis method of the alkenyl imidazole type polyion liquid gel, the preparation process of the alkenyl imidazole type polyion liquid gel is different from most reported gel synthesis methods, mainly embodies in applying electron beam radiation crosslinking technology, directly induces the generation of free radicals by utilizing high-energy electron beams emitted by an irradiation device, and initiates the polymerization and crosslinking between molecular chains, compared with the conventional chemical method, no chemical initiator and catalyst are needed to be added, and furthermore, the invention can particularly use the alkenyl imidazole type ionic liquid containing double C ═ C bonds as a functional crosslinking agent, different from the conventional chemical crosslinking agent, the alkenyl imidazole type ionic liquid containing the double C ═ C bonds can provide the crosslinking effect and can also provide the adsorption effect, thereby effectively increasing the density of adsorption functional groups, therefore, the gel has large adsorption capacity and high adsorption speed for rhenium and uranium.
4) The alkenyl imidazole type polyion liquid gel obtained by the invention has the advantages of easily available raw materials, low cost, environmental protection and no secondary pollution to the environment.
Drawings
Fig. 1 is a graph of experimental analysis of adsorption experiments of rhenium and uranium on alkenyl imidazole type polyion liquid gel prepared in example 1 under different acidity conditions.
FIG. 2 is an isothermal adsorption experiment and fitting analysis chart of rhenium and uranium respectively for the alkenyl imidazole type polyion liquid gel prepared in example 1; wherein (a) in fig. 2 corresponds to rhenium re (vii) and (b) in fig. 2 corresponds to uranium u (vi). In the figure, the concentration on the abscissa is the residual concentration (i.e., C) in the solution after the adsorption reaction is completede)。
FIG. 3 is a graph showing experimental analysis of adsorption kinetics of rhenium and uranium on the alkenylimidazole-type polyion liquid gel prepared in example 1; wherein (a) in fig. 3 corresponds to rhenium re (vii) and (b) in fig. 3 corresponds to uranium u (vi).
Fig. 4 is an experimental analysis diagram of the alkenyl imidazole polyion liquid gel prepared in example 1 for adsorption separation of rhenium from a simulated uranium ore solution.
FIG. 5 shows the repeated use of Re and U by alkenyl imidazole type polyion liquid gelThe usability; wherein (a) in fig. 5 corresponds to rhenium re (vii) and (b) in fig. 5 corresponds to uranium u (vi); in FIG. 5, any one set of columns shows the adsorption capacity (Q) from left to rightadsorption) And the amount of elution (Q)desorption)。
FIG. 6 is a Fourier infrared spectrum of an alkenylimidazole-type polyionic liquid gel prepared in example 1.
FIG. 7 is an SEM image at different magnifications of an alkenylimidazole-type polyion liquid gel prepared in example 1; in fig. 7, (a) corresponds to an enlargement by 50 times, and (b) corresponds to an enlargement by 200 times.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention is funded by the project of nuclear energy development special item (accompanying uranium resource mining and metallurgy technology-exemplified by the mining of the same Mongba-Wula-Re).
The alkenyl imidazole polyion liquid gel is obtained by polymerizing and crosslinking an imidazole ionic liquid monomer containing alkenyl and a crosslinking agent; the crosslinking agent may be selected from any one of vinyl ionic liquids and vinyl chemical crosslinking agents containing a double C ═ C bond, and preferably 1-allyl-3-vinylimidazolium salt, 3 '-divinyl-1, 1' (1, 6-hexanediyl) diimidazolium salt in ionic liquids, and a divinyl alkyl chemical crosslinking agent or a divinyl benzene chemical crosslinking agent in chemical crosslinking agents. The preparation method can be radiation crosslinking, wherein C ═ C bonds are induced to generate free radicals, and the polymerization and crosslinking between molecular chains of ionic liquid monomers and a crosslinking agent are further initiated, so that polyion liquid gel is formed. Radiation crosslinking can be specifically employed60Co gamma-rays, electron beams or X-rays, and the irradiation dose is 10-300 kGy; the gel fraction of the prepared polyion liquid gel is 60 percentThe above.
In addition, the alkenyl imidazole type ionic liquid monomer has the following structure:
Figure BDA0003570709880000061
wherein n is an integer of 1 to 12, X ═ Cl, Br, NO3,BF4,NTf2,PF6。
For example, the alkenyl-containing imidazole-type ionic liquid monomer is 1-vinyl-3-methyl-imidazole bromide, 1-vinyl-3-methyl-imidazole chloride, 1-vinyl-3-methyl-imidazole nitrate, 1-vinyl-3-methyl-imidazole tetrafluoroborate, 1-vinyl-3-methyl-imidazole hexafluorophosphate, 1-vinyl-3-methyl-imidazole bistrifluoromethylsulfinate, 1-vinyl-3-ethyl-imidazole bromide, 1-vinyl-3-ethyl-imidazole chloride, 1-vinyl-3-ethyl-imidazole nitrate, 1-vinyl-3-ethyl-imidazole tetrafluoroborate, 1-vinyl-3-methyl-imidazole tetrafluoroborate, 1-vinyl-3-ethyl-imidazole tetrafluoroborate, 1-vinyl-3-imidazole tetrafluoroborate, 1-vinyl-methyl-imidazole tetrafluoroborate, 1-vinyl-imidazole tetrafluoroborate, 1-methyl-imidazole tetrafluoroborate, 1-vinyl-3-methyl-imidazole tetrafluoroborate, 1-vinyl-3-ethyl-imidazole tetrafluoroborate, 1-vinyl-3-imidazole, 1-vinyl-3-ethyl-imidazole hexafluorophosphate, 1-vinyl-3-ethyl-imidazole bistrifluoromethylsulfinate, 1-vinyl-3-propyl-imidazole bromide.
The polymerization crosslinking reaction can be carried out in 6-80 wt% imidazole type ionic liquid aqueous solution, ethanol, methanol, DMSO or DMF solution, and the reaction temperature is normal temperature.
In addition, for rhenium-or uranium-containing solutions, rhenium or uranium is present in the solution in the form of re (vii) and u (vi) ions, respectively.
The following are specific examples:
EXAMPLE 1 preparation of Ionic liquid gels of the alkenyl imidazole type
1) Adding 1-vinyl-3-ethylimidazole bromine salt and 1-allyl-3-vinylimidazole bromine salt into 1mL of deionized water, wherein the concentrations of the two are 80% and 4.9%, respectively, after ultrasonic dissolution, pouring the uniform solution into a polyethylene bag, and using N to dissolve the uniform solution2Degassing, and sealing.
2) And (3) carrying out electron beam radiation by using an electron accelerator, so that the vinyl generates active free radicals for polymerization crosslinking reaction, and the molecular chains of reactants are induced to be polymerized and crosslinked to form the polyion liquid gel. Irradiation conditions: the irradiation voltage is 10MeV, the irradiation dose is 80kGy, and the dose rate is 10 kGy/pass. Drying the obtained gel at 50 ℃ to constant weight, soaking the gel in deionized water to remove a sol part, and drying the gel at 50 ℃ to constant weight again to obtain the polyion liquid gel with the gel fraction of 78%.
The structure of the obtained alkenyl imidazole type polyion liquid gel is as follows:
Figure BDA0003570709880000071
the structures of the reactant ionic liquids 1-vinyl-3-ethylimidazole bromide and 1-allyl-3-vinylimidazole bromide and the resulting alkenylimidazole-type polyionic liquid gel were tested by Fourier transform infrared spectroscopy (i.e., FTIR) and the results are shown in FIG. 6, in which 3060cm of the gel was 3060cm-1The left and right peaks belong to C-H vibration peak on imidazole ring and side chain of imidazole ring, 1162cm-1The peak is the characteristic peak of the imidazole ring, and the two infrared peaks exist in the spectral lines of the reactant and the gel product, which indicates that the groups have no chemical changes before and after the reaction. 1650cm-1And 1000-900 cm-1The peaks are characteristic peaks of vinyl groups in the ionic liquid, but the peaks disappear in the spectrum of the gel product, and the successful occurrence of the polymerization crosslinking reaction is proved.
In addition, the morphology of the obtained alkenyl imidazole type polyionic liquid is characterized by a scanning electron microscope (i.e. SEM), and as a result, as shown in fig. 7, the obtained alkenyl imidazole type polyionic liquid gel can be observed to have a typical three-dimensional porous network structure and large pore size.
Example 2 pH adsorption Effect test of alkenyl imidazole-type polyion liquid gel
Separately using potassium perrhenate (i.e. KReO)4) And uranyl nitrate (i.e., UO)2(NO3)2·6H2O) solid reagent is prepared into an aqueous solution containing Re and/or U required by an adsorption experiment (the following adsorption experiments are all prepared by using potassium perrhenate and uranyl nitrate reagents), and dilute acid alkali is used for adjusting the pH value to be 1-12. Weighing the prepared alkenylimidazole form10mg of the polyion liquid gel was put into 10mL of the Re or U-containing aqueous solution having the adjusted pH, and a static adsorption test was performed. The adsorption test was carried out in a 25 ℃ water bath shaker, and after 48 hours of adsorption, the clear solution was taken and the amount of adsorption of the gel (Q) was calculated by measuring the concentration of rhenium or uranium in the solution with UVe)。
The effect of pH on the adsorption of rhenium and uranium by the alkenyl imidazole polyionic liquid gel of example 1 is shown in FIG. 1. The alkenyl imidazole type polyion liquid gel can effectively adsorb rhenium and uranium within the ranges of pH 2-12 and pH 5-12 respectively.
Example 3 isotherm adsorption experiment of an alkenyl imidazole-type polyion liquid gel
10mg of an alkenylimidazole polyion liquid gel was added to 10mL of a series of rhenium solutions (natural pH) having different initial concentrations (40 to 1600ppm, specifically 40, 80, 120, 200, 300, 400, 600, 800, 1000, 1200, 1300, 1400, 1500, 1600ppm) and a series of uranium solutions (pH 7 controlled) having different initial concentrations (20 to 300ppm, specifically 20, 40, 80, 100, 120, 200, 250, 300 ppm; the initial concentration is at most 300ppm, mainly because the concentration is higher, which would cause precipitation), in a water bath oscillator at 25 ℃, after 48 hours of adsorption, a clear solution was taken, and the remaining concentration of rhenium or uranium (C) in the solution was measured by UV (C ═ 7)e) Thereby calculating the gel adsorption amount (Q)e)。
The isothermal adsorption and fitting curves of the alkenyl imidazole type polyionic liquid gel of example 1 on rhenium and uranium are respectively shown in FIG. 2, and the theoretical maximum adsorption capacities of rhenium and uranium are up to 892.9mg/g and 243.9mg/g respectively.
Example 4 kinetic adsorption experiments on alkenyl imidazole-type polyion liquid gels
Respectively adding 10mg of alkenyl imidazole type polyion liquid gel into 10mL of rhenium solution with initial concentration of 100ppm and natual pH and 10mL of uranium solution with initial concentration of 20ppm and pH of 7, respectively reacting for 1-15 min, taking out clear liquid, and detecting the residual concentration of Re or U in the solution by using UV to calculate the gel adsorption capacity (Q)e)。
The kinetic adsorption curves of the alkenyl imidazole type polyion liquid gel of example 1 on Re and U are respectively shown in fig. 3, and it can be seen that the adsorption equilibrium time on Re and U is respectively 1min and 4 min.
Example 5 adsorptive separation of rhenium from simulated uranium mine leachate using an alkenylimidazole polyionic liquid gel
Rhenium is often associated with a variety of metal ions in uranium ores, so we have formulated simulated uranium ore acid leach liquors (using anhydrous calcium chloride, magnesium chloride hexahydrate, aluminum chloride hexahydrate, iron chloride hexahydrate, sodium sulfate, sulfuric acid in addition to potassium perrhenate, uranyl nitrate) containing the following elements or species: rhenium (0.005mmol/L), uranium (0.5mmol/L), calcium (5mmol/L), magnesium (5mmol/L), aluminum (5mmol/L), iron (1mmol/L), sodium sulfate (104mmol/L) and sulfuric acid (18mmol/L), solution pH 2. 10mg of alkenylimidazole type polyion liquid gel was added to 10mL of the simulated solution, and after adsorption for 48 hours, a clear solution was taken, and the amount of adsorption of the gel (Q) was calculated by measuring the concentration of each metal ion in the solution by ICPe)。
The adsorption result of the alkenyl imidazole type polyion liquid gel of example 1 on each metal ion in the simulated liquid is shown in fig. 4, and it can be seen that the alkenyl imidazole type polyion liquid gel has good adsorption selectivity on rhenium, and does not adsorb other coexisting metal ions basically. The uranium and the rest coexisting metal ions are not adsorbed, and the main reason is that at the pH value of 2-4, the uranium and the rest coexisting metal ions are both in a cation form, and rhenium is always in an anion form, so that in the uranium ore pickling liquid with the pH value of 2, the polyion liquid gel can adsorb rhenium and not adsorb the rest metal ions. Especially for rhenium and uranium, the +7 valence rhenium element is ReO in an aqueous system4 -The anion exists (no matter the pH value condition); while the +6 valent uranium element may be present in the anionic form (i.e., (UO)2)3(OH)7 -Or UO2(OH)3 -) May also exist in a cationic form (i.e., UO)2 2+、(UO2)3(OH)5 +、UO2OH+Or (UO)2)4(OH)7 +) The form of the complex ion of the + 6-valent uranium element changes with the change of pH, for example, the uranium element is a cation at a pH of 1 to 4, both an anion and a cation at a pH of 4 to 10, and an anion at a pH of 10 to 12. As can be seen from FIG. 4, when the pH value is 2-4, the polyion liquid gel has a selective adsorption effect on rhenium.
Example 6 reproducible experiments on alkenyl imidazole-type polyion liquid gels
Respectively adding 10mg of alkenyl imidazole type polyion liquid gel into 10mL of rhenium solution with initial concentration of 200ppm and natural pH and 10mL of uranium solution with concentration of 100ppm and pH of 7, washing with deionized water for three times after adsorption is finished, and respectively using 3mol/L HNO3And 0.1mol/L HCl eluted rhenium and uranium on the gel. The gel after each adsorption and elution experiment was washed three times with deionized water and then subjected to the next cycle. This was repeated five times. Collecting the supernatant after adsorption and elution, and detecting the concentration of Re or U in the solution with UV to calculate the adsorption amount (Q)adsorption) And the amount of elution (Q)desorption)。
The results of adsorption-desorption of rhenium and uranium by the alkenylimidazole-type polyionic liquid gel of example 1 are shown in fig. 5, and it can be seen that the gel has good reusability.
Example 7 Effect of irradiation dose on preparation and Properties of alkenyl imidazole-type polyion liquid gels
Preparing a series of uniformly mixed aqueous solutions containing 80% 1-vinyl-3-ethylimidazole bromine salt and 4.9% 1-allyl-3-ethylimidazole bromine salt, filling the aqueous solutions into a polyethylene bag, and adding N2After the hermetic sealing is removed, an electron accelerator with energy of 1MeV and 10MeV is used for irradiation to different absorption doses (up to 300kGy), effective gel products can be obtained, alkenyl imidazole type polyion liquid gel with gel fraction of more than 60% can achieve equivalent adsorption experiment results on rhenium and uranium.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (9)

1. The application of the polyion liquid gel material in the adsorption separation of rhenium and/or uranium is characterized in that the rhenium element Re with the valence of +7+7And/or the + 6-valent uranium element U+6The existing form in the aqueous solution comprises anions, and the polyion liquid gel material is specifically alkenyl imidazole type polyion liquid gel, and the structural formula of the polyion liquid gel is shown as the following formula:
Figure FDA0003570709870000011
in the formula, m and n are independently selected from integers between 1 and 12; x ═ Cl, Br, NO3,BF4,NTf2,PF6；
The application is specifically that the alkenyl imidazole type polyion liquid gel is added into a solution to be treated so as to carry out adsorption and enable the solution to contain Re+7And/or contain U+6The anions of (2) are adsorbed to the polyion liquid gel material to realize adsorption separation.
2. The use according to claim 1, wherein the solution to be treated contains the rhenium element; before application, firstly, regulating the pH value of a solution to be treated to 2-12; when in use, the polyion liquid gel material can adsorb Re-containing materials+7The anion of (2) to effect separation of rhenium from the solution.
3. Use according to claim 1, characterized in that the solution to be treated contains uranium; before application, firstly, regulating and controlling the pH value of a solution to be treated to be 5-12; when in use, the polyion liquid gel material can adsorb U-containing substances+6The uranium is separated from the solution.
4. The use according to claim 1, wherein the solution to be treated is the same as the solution to be treatedThe material contains rhenium element and uranium element; when the method is applied, the pH value of a solution to be treated is regulated to 2-4; when in use, the polyion liquid gel material can selectively adsorb Re-containing materials+7The rhenium and the uranium are separated;
preferably, the solution to be treated is uranium ore leaching liquid.
5. The use according to claim 1, further comprising, after completion of the adsorption, eluting and separating the polyion liquid gel material adsorbed with the target anion by using an eluent to regenerate the polyion liquid gel material; the regenerated polyion liquid gel material can be repeatedly applied to rhenium and/or uranium adsorption separation;
preferably, the eluent is HNO with the concentration of 0.1-4 mol/L3Solution or HCl solution with the concentration of 0.1-4 mol/L.
6. The use according to claim 1, wherein the alkenyl imidazole-type polyionic liquid gel is obtained by polymerizing and crosslinking an alkenyl-containing imidazole-type ionic liquid monomer and a crosslinking agent; wherein the content of the first and second substances,
the cross-linking agent is selected from any one of alkene ionic liquid containing double C-C bonds and alkene chemical cross-linking agent containing double C-C bonds; preferably, the vinyl ionic liquid containing a double C ═ C bond is 1-allyl-3-vinylimidazolium salt, or 3,3 '-divinyl-1, 1' (1, 6-hexanediyl) diimidazolium salt; the alkene chemical cross-linking agent containing double C ═ C bonds is a divinyl alkyl chemical cross-linking agent or a divinyl benzene chemical cross-linking agent;
the polymerization crosslinking is specifically radiation crosslinking, and is to generate free radicals by inducing C ═ C bonds, and then further initiate polymerization and crosslinking between molecular chains of ionic liquid monomers and crosslinking agents, so that polyion liquid gel is formed.
7. The use according to claim 6, wherein the alkenyl-containing imidazole-type ionic liquid monomer is 1-vinyl-3-methyl-imidazolium bromide, 1-vinyl-3-methyl-imidazolium chloride, 1-vinyl-3-methyl-imidazolium nitrate, 1-vinyl-3-methyl-imidazolium tetrafluoroborate, 1-vinyl-3-methyl-imidazolium hexafluorophosphate, 1-vinyl-3-methyl-imidazolium bistrifluoromethylsulfinate, 1-vinyl-3-ethyl-imidazolium bromide, 1-vinyl-3-ethyl-imidazolium chloride, 1-vinyl-3-ethyl-imidazolium nitrate, 1-vinyl-3-methyl-imidazolium chloride, or mixtures thereof, 1-vinyl-3-ethyl-imidazole tetrafluoroborate, 1-vinyl-3-ethyl-imidazole hexafluorophosphate, 1-vinyl-3-ethyl-imidazole bistrifluoromethylsulfinate, 1-vinyl-3-propyl-imidazole bromide.
8. The use according to claim 6, wherein the cross-linking reaction is carried out in aqueous solution, ethanol, methanol, DMSO or DMF solution at room temperature; before polymerization crosslinking occurs, the concentration of the imidazole type ionic liquid monomer containing alkenyl in a solution system is 6-80 wt%.
9. The use as claimed in claim 6, wherein said radiation crosslinking is carried out by60Co gamma-rays, electron beams or X rays, wherein the irradiation dose is 10-300 kGy; the gel fraction of the polyion liquid gel obtained correspondingly is more than 60%.
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CN115591272A (en) * 2022-10-27 2023-01-13 大连科利德光电子材料有限公司（Cn） Method and system for purifying silicon-based precursor
CN115591272B (en) * 2022-10-27 2023-04-07 大连科利德光电子材料有限公司 Method and system for purifying silicon-based precursor

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